text:
A method and apparatus for evaporating a solid organic material by sublimation using an infrared guiding heater which minimizes temperature gradients in the bulk of the organic target. The bulk is heated to a temperature below the sublimation temperature of the target. A localized area of the target is sublimated by the infrared guiding heater while regulating the temperature of the bulk. The vapor is then deposited over, and condensed on, a substrate to form a solid organic layer.
1. A method, comprising:
(a) providing a target consisting of a solid organic material;
(b) heating a bulk of the solid organic material to a first temperature using a first heat source, the first temperature being below a sublimation temperature of the solid organic material;
(c) sublimating a localized portion of the target by selectively heating the localized portion to a second temperature at or above the sublimation temperature using a second heat source;
(d) transporting the sublimated organic material from the target to a substrate; and
(e) depositing the sublimated organic material over the substrate to form a layer comprising the solid organic material.
2. The method of
3. The method of
4. The method of
5. The method of
6. The method of
(c1) selectively targeting infrared energy onto the localized portion to selectively heat said localized portion to the second temperature.
7. The method of
(f) scanning the infrared energy across a surface of the target.
8. The method of
(c2) focusing the infrared energy to control a cross-sectional area of the infrared energy at a surface of the target.
9. The method of
10. The method of
spectroscopically detecting impurities in the sublimated organic material indicative of decomposition; and
responsive to detecting impurities in the sublimated organic material by performing at least one of:
lowering said first temperature of the bulk;
adjusting a cross-sectional area of targeted infrared energy applied to the localized portion to sublimate the solid organic material;
adjusting an intensity of targeted infrared energy applied to the localized portion to sublimate the solid organic material;
adjusting a duration of an infrared pulse applied to the localized portion to sublimate the solid organic material; and
changing a targeting of infrared energy applied to the target to sublimate the solid organic material to avoid an area of a surface of the target from which the impurities originated.
11. The method of
monitoring a sublimation rate of the solid organic material; and
responsive to a change in the sublimation rate, performing at least one of:
lowering said first temperature of the bulk;
adjusting a cross-sectional area of targeted infrared energy applied to the localized portion to sublimate the solid organic material;
adjusting an intensity of targeted infrared energy applied to the localized portion to sublimate the solid organic material;
adjusting a duration of an infrared pulse applied to the localized portion to sublimate the solid organic material; and
changing a targeting of infrared energy applied to the target to sublimate the solid organic material to avoid an area of a surface of the target from which the impurities originated.
12. The method of
measuring temperature at a surface of the solid organic material by radiometry; and
responsive to the measured temperature, performing at least one of:
lowering said first temperature of the bulk;
adjusting a cross-sectional area of targeted infrared energy applied to the localized portion to sublimate the solid organic material;
adjusting an intensity of targeted infrared energy applied to the localized portion to sublimate the solid organic material;
adjusting a duration of an infrared pulse applied to the localized portion to sublimate the solid organic material; and
changing a targeting of infrared energy applied to the target to sublimate the solid organic material to avoid an area of the surface of the target from which the impurities originated.
13. An apparatus, comprising:
a deposition chamber adapted to have a substrate disposed therein;
a target site adapted to receive a target, such that material evaporated from the target deposits on the substrate;
a bulk heater adapted to heat a bulk of the target at the target site; and
an infrared guiding heater comprising:
an infrared source; and
optical components adapted to direct energy from the infrared source onto a surface of the target and thereby evaporate the material.
14. The apparatus of
a focusing lens to focus the energy from the infrared source and control a cross-sectional area of the energy at the surface of the target.
15. The apparatus of
a diffractive optic adapted to reshape an intensity profile of the energy, positioned in an optical path of the energy between the infrared source and the focusing lens.
16. The apparatus of
a collimator.
17. The apparatus of
a targeting element in an optical path of the energy between the infrared source and the target, adapted to alter an optical path of the energy and thereby select a location where the energy strikes the surface of the target; and
the apparatus further comprising at least one electromechanical actuator to displace the targeting element to alter the optical path,
wherein the targeting element is selected from the group consisting of a mirror and a prism.
18. The apparatus of
19. The apparatus of
a radiation detector positioned to receive energy radiated from the target; and
a signal processor to calculate a surface temperature of the target based upon the radiated energy received by the radiation detector.
20. The apparatus of
a photodetector adapted to measure an absorption spectra of the material evaporated from the target; and
a signal processor to detect impurities in the material evaporated from the target indicative of decomposition based upon the absorption spectra measured by the photodetector.
21. The apparatus of
wherein the infrared source is selected from the group consisting of a carbon heater, a halogen lamp heater, a shortwave-infrared heater, a xenon lamp, and a laser.
The present invention relates to organic material deposition systems used to fabricate organic light emitting devices (OLEDs), and more specifically to systems for vapor deposition by sublimation.
Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.
OLEDs make use of thin organic films that emit light when voltage is applied across the device. Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an �exciton,� which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
Material impurities and defects in the organic layers increase non-radiative decay mechanisms and increase material reabsorption of photoemissions, resulting in an increase in heat generation, a lowering of the internal quantum efficiency, and a decrease in the life of the device.
A mechanism which produces defects during layer deposition is thermal decomposition. Thermal decomposition occurs when thermal energy causes bonds within organic molecules or chains to disassociate, breaking the organic material down into constituent components. The constituent components may also produce outgassing and secondary reactions. Thermal decomposition also alters the vaporization rate of the organic material used to form the organic layer.
Methods have been developed to reduce thermal decomposition and to improve the controllability of the vaporization rate. For example, U.S. Pat. No. 6,797,337 to Dando et al. (�Dando�) discloses a method for reactively growing metallic layers by evaporating a metal organic precursor.
In Dando, a solid precursor comprising an organic metal-containing compound is vaporized by exposing a large area of the surface of the precursor to infrared radiation, sublimating the precursor at the surface without the necessity of heating the entire volume. A non-reactive carrier gas then transports the vaporized precursor to a reaction chamber containing a substrate. In the reaction chamber, the vaporized precursor undergoes a chemical reaction when mixed with separately injected chemical species, whereupon the desired metal is deposited on the substrate.
Many solid precursors decompose over time when held near their sublimation temperatures, especially if the decomposition temperature is below the sublimation temperature. By minimizing the heating of the bulk, Dando seeks to minimize bulk decomposition and thereby gain better control over the vaporization rate.
To sublimate a solid it is necessary to impart sufficient energy to transition the solid directly into vapor without melting. In the system of Dando, this can require a relatively large amount of energy to overcome the large temperature gradient between the bulk and the surface, which may result in decomposition of the organic material in the vapor. Vapor decomposition is of little consequence, since the precursor in Dando is purposely unstable, undergoing a chemical reaction prior to deposition and having some constituent components discarded in the reactor.
While the system of Dando does have some advantages for precursor-based deposition of films, it may not be well suited to precursor-free systems. Precursor-free systems vaporize a solid organic material, having the vapor condense on a substrate to assemble into a layer of solid organic material having the same molecular composition as the original target material. The absence of precursor components eliminates a source of contamination in the assembled organic layer. However, decomposition of either the bulk or the vapor diminishes the quality of the assembled organic layer and can compromise the operational efficiency of a finished device.
Another problem that may occur in the system of Dando is material instability produced by thermal cycling. While it is generally efficient to use a same target to create multiple layers, each time heating is suspended, residual energy from the surface dissipates into the bulk. These thermal oscillations can create molecular instability in solid organic materials sensitive to thermal history. Even when this instability does not create decomposition in the bulk, it can increase the likelihood of decomposition in the vapor.
An example of another method to reduce thermal decomposition and to improve the controllability of the vaporization rate is disclosed in U.S. Pat. No. 5,094,880 to Hongoh (�Hongoh�). Hongoh discloses a precursor-free system for the deposition of organic superconductor materials. Organic superconducting materials are particularly unstable, in comparison to inorganic semiconductors and insulators. Organic superconducting materials have relatively low sublimation temperatures and heat resistance and are prone to decomposing immediately upon vaporization by ordinary methods. Hongoh irradiates an actively cooled target with focused light energy to instantaneously heat a small surface portion of the target to sublimation. The energy density of the light is restrained to minimize decomposition of the material. Breakdowns in molecular structure are further reduced by applying pulsed light to shorten the heating time.
While the method of Hongoh offers several improvements over Dando, the temperature gradient at the surface of the cooled target in combination with the restraints on energy density results in a very slow deposition process. For the mass-manufacturing of organic components such as OLEDs, such a slow process is commercially impractical.
In certain embodiments of the invention, the bulk of a solid organic target is heated and a localized surface portion of the target is sublimated by selective heating. By heating the bulk, the temperature gradient between the bulk and the localized surface portion is minimized, facilitating rapid sublimation while minimizing the selectively applied energy needed to transition the solid organic material directly to vapor. Localized infrared heating need only provide enough additional energy to sublimate the stable evaporant, rather than to having to overcome a large temperature gradient in the localized surface region.
The wavelength of the localized heating may be selected to minimize penetration of the bulk by infrared energy sublimating the localized portion. This is accomplished by selecting a wavelength with a very high absorption coefficient in the target material.
The effects of thermal cycling are minimized by maintaining the bulk temperature over an extended period of hours or days. The bulk is heated to a �safe� temperature at which substantially no thermal decomposition occurs for an extended time. Since the decomposition-effect of heating is cumulative, the �safe� temperature is selected to offset the duration that bulk heating will be maintained.
By maintaining the organic material at a safe temperature, there is less contamination of the surface as compared with an organic material that is held at its sublimation temperature for an extended period of time. This means the surface may be kept clean and uncontaminated with decomposition products, so that sublimation may continuously take place from a fresh clean surface for a much longer period of time. In addition, the system can be kept at a high vacuum with much higher purity levels than when decomposition products are present on the surface.
Impurities introduced by precursor byproducts are eliminated by sublimating a solid target material which does not comprise a precursor. The target organic material that undergoes sublimation is deposited on the substrate without undergoing a chemical reaction, either by itself, or together with other materials such as dopants.
In other embodiments of the invention, the bulk of the solid organic target may not need to be heated, for example, whenever the size and temperature of the localized heating is controlled precisely enough to prevent decomposition. Such a method may be suitable for organic materials that do not so readily decompose at temperatures near the sublimation temperature.
The figures are not drawn to scale.
Specific representative embodiments of the invention will now be described, including how such embodiments may be made. It is understood that the specific methods, materials, conditions, process parameters, apparatus and the like do not necessarily limit the scope of the invention.
The target 120 is placed in an evaporation chamber 200 to be sublimated by infrared guiding heater 110. An inert, non-reactive gas (e.g., nitrogen, helium, argon, krypton, xenon, neon) flows into inlet 262 of the evaporation chamber 200, transporting the organic vapor to a deposition chamber 260 via a conduit 264. The organic vapor and carrier gas pass through a �shower� head 266, depositing the organic material on the substrate 130. The carrier gas then exits the deposition chamber 260 through an outlet 268. The pressure within the system may be, for example, between 0.001 and 100 Torr. Further discussion of OVPD can be found, for example, in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference.
Referring to both embodiments, the walls of deposition chamber 100, evaporation chamber 200, and conduit 264 may be heated to inhibit layer formation on the chamber walls and to promote transport of the vapor. The deposition chamber 260 in the OVPD system may also be heated. The deposition chamber 100/260 may include an adjustable mount 134 to hold substrate 130 that may be rotated during deposition to promote formation of an even layer. The mount 134 may also allow adjustment of the distance between the substrate 130 and the target 120, or the substrate 130 and the head 266. Chamber windows 102/202 are made of a material transparent to infrared such as quartz.
The target 120 may be crystalline, poly-crystalline, amorphous, or powdered, and may be in the form of a pellet. Typical crucibles are one-to-three inches (2.5 to 7.6 centimeters) in diameter, although other sizes may be used.
The bulk of the target 120 is held at a temperature that minimizes gradients during surface heating while producing substantially no thermal decomposition over time. Since decomposition is a cumulative effect, the exact temperature for any given material depends upon how long the target will be held at a specified bulk temperature, the sublimation temperature of the material, and the thermal stability of the material. The target may be held at the specified temperature for at least twenty-four hours, or for some processes, at least six days. For organic materials having a sublimation temperature of about 200 and 400 degrees Celsius, an example of a bulk temperature is at least 100 degrees Celsius, but preferably at least 50 degrees Celsius less than the thermal decomposition temperature of the solid organic material at which decomposition spontaneously occurs. For materials with a sufficiently high decomposition temperature, the bulk temperature is preferably held within 10 to 50 degrees Celsius of the sublimation temperature.
The bulk heater 126 used to heat the target 120 may use any known method appropriate for organic materials. For example, bulk heater 126 may be an infrared heater, an electric coiled heating element (e.g., contact heater), a radio frequency (RF) heater, and an electromagnetic (EM) dielectric heater (heating either the bulk of the target 120 or the crucible 126). Examples of infrared heaters include carbon heaters, halogen lamp heaters, shortwave-infrared heaters, and xenon lamps. Examples of contact heaters include a coiled wire heated by a flow of electric current. Examples of RF heaters and EM dielectric heaters include coils.
Indirect heating may be used to heat the crucible 124 to heat the target 120. By using a crucible materials that absorbs infrared energy, RF, or EM and converts it to heat, energy applied to crucible 124 may be used to heat the target 120 by conduction. Likewise, if the crucible is thermally conductive, heat applied to the crucible 124 by a contact heater is conducted to the target.
Direct heating also may be used to heat the target 126. For example, infrared energy may be applied directly to the target 120, if the crucible 124 is transmissive to infrared energy (e.g., quartz or Pyrex). Since solid organic targets will absorb most of the infrared energy near the surface (i.e., low penetration), the infrared energy must be fairly low and rely upon thermal conduction to avoid decomposing the incident surface. Likewise, EM dielectric heating may be used to directly heat the target 120.
Preferably, for either direct or indirect heating, the energy applied by the bulk heater 126 should not produce a localized temperature in the target 120 more than 10 degrees greater than the temperature to be maintained in bulk. Heat or energy may be applied from multiple sides of the bulk, may be applied from the surface opposite the sublimation surface, and/or may be applied from the sublimation surface. Although bulk heater 126 is illustrated within chamber 100/200, it may also be an external device.
Carrier gas preheating in OVPD may contribute to the temperature of the bulk, but it is not considered suitable as a means for bulk heating because the temperature of the carrier gas is regulated primarily to control the vapor pressure of the target material in the carrier gas, rather than the temperature of the target 120 itself. As a result, carrier gas preheating may not have enough flexibility to maintain a particular temperature in the bulk with sufficient precision to achieve the desired results.
By minimizing the temperature gradient between the sublimated material and the bulk, organic material can be vaporized quickly with minimal energy. The present localized heating method is particularly suitable for organic materials that may decompose at temperatures at or near the sublimation temperature. The decomposition temperature is preferably sufficiently higher than the sublimation temperature such that the organic material may be vaporized at a high rate without causing significant decomposition. However, if there is only a relatively small difference between the sublimation temperature and the decomposition temperature, the spot size and the temperature of the spot may be precisely regulated, in combination, to produce the desired sublimation rate without causing significant decomposition. For example, if the decomposition temperature is only about 15 degrees Celsius higher than the sublimation temperature, the energy applied to the localized portion by the infrared heater 110 preferably raises the temperature of the organic material to not more than about 10 degrees Celsius higher than the sublimation temperature. In this case, if a high sublimation rate is desired, the spot size may be increased sufficient to produce the desired sublimation rate.
During deposition, feedback is used to regulate sublimation to avoid any significant quantity of decomposed material being deposited on the substrate. There may be a significant difference in the evaporation rate of organic molecules and their decomposed constituents. There may also be a difference in thermal and chemical properties between intact and decomposed materials. When decomposed material is detected, either directly or indirectly, a variety of mitigation responses may be applied, including: lowering the temperature of the bulk; adjusting a cross-sectional area of the infrared light 112 irradiating the localized portion 122; adjusting an intensity of the infrared light 112; adjusting the duration of infrared pulses if the infrared light 112 is pulsed; and changing a targeting of the infrared light 112 on the surface of the target 120 to avoid the area from which decomposed material originated.
A first type of feedback that may be employed is to monitor the deposition rate using an in-situ crystal monitor 132. A change in the deposition rate corresponds to a change in the evaporation rate, which may indicate a transition between intact and decomposed material. Examples of crystal monitors may be found, for example, in U.S. Pat. No. 4,579,083 to Boivin and U.S. Pat. No. 5,233,261 to Wajid, which are incorporated herein by reference.
A second type of feedback is absorption spectroscopy to monitor the presence of decomposition impurities in the organic vapor. The molecules in the vapor absorb optical energy, converting the absorbed energy into vibration. Different molecules and bonds have different vibrational states. A plurality of optical wavelengths are produced by optical emission source 150 to be detected by photo-detector 152. By calibrating the system to account for the vibrational energy already present due to sublimation, and measuring the percentage of energy across an optical spectrum which is transmitted through the vapor, a determination can be made as to which wavelengths are absorbed and which wavelengths are transmitted. As intact and decomposed materials have different absorption wavelengths, the presence or absence of decomposed material can be determined.
The optical emissions from source 150 may be infrared, although depending upon materials, other wavelengths might be used. To minimize any contribution to decomposition that may be caused by the energy introduced by spectroscopy, the optical energy introduced by source 150 should be minimized. Additionally, the source 150/detector 152 combination may be placed adjacent to the path between target 120 and the substrate 130 (VTE or OVPD), or at a chamber outlet 268 (OVPD), to decrease the likelihood that the vapor sampled will be included in the deposited layer. Additionally, to increase resolution, the optical energy may be reflected through the vapor one-or-more times before reaching detector 152. A representative spectroscopy system is demonstrated in U.S. Pat. No. 5,801,826 to Williams, which is incorporated herein by reference. A method relevant to calibration of the absorption spectra of an organic material subject to decomposition is disclosed in U.S. Pat. No. 6,794,649 to Thrash et al., which is incorporated herein by reference. Other types of spectrometers may be used, including miniature integrated mass spectrometers, either in-situ or at an outlet 268.
A third type of radiometry feedback uses radiation detector 140 to determine the temperature at the localized portion and to detect decomposed material at the surface of the target. This feedback technique is well suited to embodiments employing a pulsed infrared guiding heater. After the surface of the target is heated by an infrared guiding heater 110 (or 810 in
Another radiometry technique to measure thermal properties of the target 120 includes an acousto-optic modulator in the infrared guiding heater to vary the phase of pulsed laser light and measures changes in the amplitude and phase of IR emissions from the target; see U.S. Published Application 2002/0011852 A1 to Mandelis et al., which is incorporated herein by reference. A variation on this technique can be performed with continuous-wave laser light by including an acousto-optic modulator in the infrared guiding heater to modulate the IR light, and by including a filter on radiation detector 140 to block the wavelength of reflected the IR light, while passing the wavelengths of other emissions from the target.
A fourth type of feedback that can be used to select areas for targeting with the infrared guiding heater is passive thermographic imaging of the surface of the target 120. Relative differences in the quantity of the radiation emissions from the surface of the bulk can be used to identify uneven heating due to, for example, geometric changes to the surface profile of the target 120 or patches of decomposed material.
The optical waveguide may be a quartz guiding rod 345, guiding light by total internal reflection. The optical waveguide might also be a collimator formed, for example, from a bundle of quartz tubes, or a bundle of graded-index or step-index optical fibers made from a material with low infrared absorption. Examples of infrared source 315 include incoherent sources such as a carbon heater, a halogen lamp heater, a shortwave infrared heater, and a xenon lamp. The infrared source may also be a coherent source such as a continuous wave or a pulsed laser.
Light from the waveguide is then focused using focusing lens 355 as an embodiment of heater 110. Additional optic elements may be included to adjust the focus so that the diameter of the infrared light incident on the target can be adjusted to control a cross-sectional area of the energy at the surface of the target.
The light 112 from the guiding heater 110/310/410/510 may be focused so that that the localized portion 122 is equivalent to less than 50% of the initial exposed area of the target 120 available for sublimation, prior to an initiation of sublimation. With this large incident exposure, the surface of the target may be scanned in a circular fashion. For tighter control, the light 112 from the guiding heater may be focused so that the localized portion 122 is equivalent to less than 10% of the initial exposed area of the target 120 available for sublimation, prior to an initiation of sublimation.
While pulses having a duration in the range of milliseconds may have advantages for overcoming a signal-to-noise ratio for radiometry, shorter pulses have the advantage of producing less conductive heating in the target 120. For examples, picosecond and femtosecond infrared pulses are generated over a broad infrared spectral range by J. M. Liu, �Nonlinear generation of ultrashort infrared pulses,� IEEE LEOS '94 Conference Proceedings, Vol. 2, pp. 90-91 (1994). However, since little heat is produced by such short pulses, radiometric temperature measurement may be rendered ineffective. Therefore, while very short pulses can be advantageous for avoiding decomposition in the bulk, it is important that the pulse energy is sufficiently low so that only inter-molecular (not intra-molecular) bonds are broken during sublimation.
Additionally, the intensity profile of the infrared spot 612 on the surface of the target 120 may be shaped to minimize surface heating. For example, as shown in
In response to the input data, the signal processor/controller 900 may adjust one or more of the electromechanical actuator 567 selecting the location of the localized portion 122 on the surface of the target 120; a focus adjustment 912 controlling the size of the incident spot 612 and the size of the localized portion 122; the temperature produced by the bulk heater 126; an intensity control 914 of the IR source 315; a pulse rate control 916 of either the IR source 315 or a shutter; a valve control 918 controlling the flow of carrier gas in the OPVD embodiment; and/or a temperature control 920 of a carrier gas preheater in the OVPD embodiment. The Z-axis position of the substrate may also be adjusted.
In addition to conventional VTE and OVPD, the concepts of the invention may be applied to other organic vapor delivery techniques. For example, the concepts of the invention can be used with organic molecular beam vapor deposition (OMVD), which is a flavor of molecular beam epitaxy (MBE). As an OMVD embodiment of the invention, an effusion cell (evaporant source) comprises the target 120, crucible 124, bulk heater 126, and infrared guiding heater 110. The OMVD embodiment may also employ the various feedback elements of the invention (e.g, radiation detector 140, IR source 150, photodetector 152, and crystal monitor 132).
Examples of organic target materials that might be evaporated in the embodiments of present invention include organic and organometallic materials. The organic materials may or may not contain metal atoms. The organic material may be a small molecule material, although other materials, such as monomers, oligomers, or dendrimers, may also be used.
As used herein, the term �organic� includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. �Small molecule� refers to any organic material that is not a polymer, and �small molecules� may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the �small molecule� class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be an fluorescent or phosphorescent small molecule emitter. A dendrimer may be a �small molecule,� and it is believed that all dendrimers currently used in the field of OLEDs are small molecules. In general, a small molecule has a well-defined chemical formula with a single molecular weight, whereas a polymer has a chemical formula and a molecular weight that may vary from molecule to molecule.
The term �organometallic� as used herein is as generally understood by one of ordinary skill in the art and as given, for example, in �Inorganic Chemistry� (2nd Edition) by Gary L. Miessler and Donald A. Tarr, Prentice Hall (1998). Thus, the term organometallic refers to compounds which have an organic group bonded to a metal through a carbon-metal bond. This class does not include per se coordination compounds, which are substances having only donor bonds from heteroatoms, such as metal complexes of amines, halides, pseudohalides (CN, etc.), and the like. In practice organometallic compounds generally comprise, in addition to one or more carbon-metal bonds to an organic species, one or more donor bonds from a heteroatom. The carbon-metal bond to an organic species refers to a direct bond between a metal and a carbon atom of an organic group, such as phenyl, alkyl, alkenyl, etc., but does not refer to a metal bond to an �inorganic carbon,� such as the carbon of CN or CO.
Examples of organic materials that might be evaporated include: CBP (4,4′-N,N-dicarbazole-biphenyl); m-MTDATA (4,4′,4″-tris(3-methylphenylphenlyamino)triphenylamine); Alq3 (8-tris-hydroxyquinoline aluminum); Bphen (4,7-diphenyl-1,10-phenanthroline); n-BPhen (BPhen n-doped with lithium); F4-TCNQ (tetrafluoro-tetracyano-quinodimethane); p-MTDATA (m-MTDATA p-doped with F4-TCNQ); Ir(ppy)3 (tris(2-phenylpyridine)-iridium); Ir(ppz)3 (tris(1-phenylpyrazoloto,N,C(2′)iridium(III)); BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline); TAZ (3-phenyl-4-(1′-naphthyl)-5-phenyl-1,2,4-triazole); CuPc (copper phthalocyanine); NPD (N,N′-diphenyl-N�N′-di(1-naphthyl)-benzidine); TPD (N,N′-diphenyl-N�N′-di(3-toly)-benzidine); BAlq (aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate); mCP (1,3-N,N-dicarbazole-benzene); DCM (4-(dicyanoethylene)-6-(4-dimethylaminostyryl-2-methyl)-4H-pyran); and DMQA (N,N′-dimethylquinacridone). These materials are merely examples, as the invention is not so limited.
Doping may be used to enhance conductivity in the deposited layer. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in United States Patent Application Publication No. 2002-0071963 A1 to Forrest et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, which is also disclosed in United States Patent Application Publication No. 2002-0071963 A1 to Forrest et al.
The materials and methods described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, fabrication of organic devices, such as organic transistors, may employ the disclosed materials and methods.
Another embodiment of the invention includes the features of the other embodiments described above, but omits an element specifically directed to thermal management of the bulk of the target 120 (i.e. the bulk is neither actively heated nor cooled, omitting bulk heater 126). Active heating or cooling may be desirable because it gives more precise control over the temperature of the bulk. However, in some implementations, high precision temperature control may not be needed and it may be preferable to avoid expense and extra equipment associated with active heating or cooling.
Incidental heating of the bulk of the target 120 may still occur because of carrier gas preheating (OVPD) and thermal conduction of energy from the incident light 112/812. Even though there is no active heating or cooling, the thermal gradients at the localized portion may be minimized by actively regulating the incident energy. For example, utilizing feedback and adjusting a cross-sectional area of the targeted infrared energy, adjusting the intensity of the targeted infrared energy, adjusting the duration of an infrared pulse, and/or changing a targeting of the infrared energy to avoid a decomposed area of the surface of the target. Decomposition may also be reduced by minimizing energy conducted into the bulk by shaping the intensity profile of the incident spot to avoid lateral heating without sublimation. Further, if OVPD, the effects of thermal cycling may be mitigated by avoiding abrupt temperature fluctuations in the preheating of the carrier gas.
It is understood that various theories as to why the invention works are not intended to be limiting.
While the present invention is described with respect to particular examples and preferred embodiments, it is understood that the present invention is not limited to these examples and embodiments. The present invention as claimed therefore includes variations from the particular examples and embodiments described herein, as will be apparent to one of skill in the art.
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I find myself going to Kickstarter and Indiegogo on a regular basis these days because they have become real innovation marketplaces. As far as I'm concerned, this is where a lot of cool ...

subset: commoncrawl


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Napoleon told to reimburse Wayne County $18,186
Staff for Sheriff Benny Napoleon say he's being unfairly treated.
Wayne Co. Commission votes down Mound Rd. jail
Wayne County Commissioners have now formally passed a resolution that takes the option of moving the jail to a Mound Road facility on…
Napoleon defends using public money in campaign
Sheriff Benny Napoleon lost when he ran last year for Detroit Mayor, and he wasn't alone. Wayne County taxpayers didn't…
EMU beefing up security on campus
At 23, Julia Niswender was just getting started. "We are aggravated--frustrated," says stepfather Jim Turnquist, stepfather of the…
Mom says pleas to help suicidal child go ignored
"I feel like I'm in this vicious cycle, we're both caught in this vicious cycle that never ends," says the boy's mom.
Wayne Co. Commission: Don't move jail to Mound
Wayne County Commissioners have passed a resolution that takes the option of moving the jail to Detroit's east side off the table.
Watergate editor Ben Bradlee dies
At The Washington Post and beyond, he was legendary.
Report: Toys R Us removes Breaking Bad toys
Toys R Us customers won't be able to buy Breaking Bad action figures at the stores after all.
Indiana police contacted about potential killer in 2010
A string of unsolved strangling cases from the early 1990s to 2007 sit in the files at the Gary, Indiana police department. Four years ago,…
Should the Fed tackle economic inequality?
Janet Yellen gave a speech last week that was unusual for a sitting chair of the Federal Reserve, though it doesn't seem to have gotten…
Pack of smokes with that prescription?
Talk about a prescription for trouble. One in 20 pharmacy patients picking up a prescription to treat asthma, chronic obstructive pulmonary…
3 things to know about Ebola
Ebola has dominated the headlines. But here are three things to know about the disease.


text: ESPN Feed: pekka rinne http://assets.espn.go.com/i/tvlistings/tv_espn_original.gif ESPN en-us 10 ESPN Inc. http://espn.go.com/ Copyright 2010 ESPN Inc. Canucks lead series 1-0 Roberto Luongo stopped all 20 Nashville shots for his third career playoff shutout. The host Canucks won their sixth ...]]> April 28, 2011 22:44:41 PDT Vancouver's Roberto Luongo, Nashville's Pekka Rinne and Boston's Tim Thomas were named the finalists for this year's Vezina Trophy today. Scott Bur...]]> April 22, 2011 09:32:03 PDT


text: If your ever visit GOA, you must eat at Florentine's. Chicken Cafreal without any question was the best Cafreal I ever had. I don't remember what other dish I had at Florentine's but Chicken Cafreal. My friend visited GOA thrice and missed on Chicken Cafreal due to bad timings as Florentine's very strict about working hours. They are open from... More


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1. I take my dog for a walk on Saturdays in the big park by the lake. I do this very early in the morning before children come to the park. That way I can let my dog run freely. He jumps out the minute I open the car door and soon sees the first innocent squirrel. Then he is off like a shot and doesn't stop running for at least half an hour.
2. Lola hates huge tractor trailers that sometimes tailgate her Honda Civic. The enormous smoke-belching machines seem ready to swallow her small car. She shakes her fist at the drivers, and she rips out a lot of angry words. Recently she had a very satisfying dream. She broke into an army supply depot and stole a bazooka. She then became the first person in history to murder a truck.
3. When I sit down to write, my mind is blank. All I can think of is my name, which seems to me the most boring name in the world. Often I get sleepy and tell myself I should take a short nap. Other times I start daydreaming about things I want to buy. Sometimes I decide I should make a telephone call to someone I know. The piece of paper in front of me is usually still blank when I leave to watch my favorite television show.
4. One of the biggest regrets of my life is that I never told my father I loved him. I resented the fact that he had never been able to say the words "I love you" to his children. Even during the long period of my father's illness, I remained silent and unforgiving. Then one morning he was dead, with my words left unspoken. A guilt I shall never forget tore a hole in my heart. I determined not to hold in my feelings with my daughters. They know they are loved, because I both show and tell them this. All people, no matter who they are, want to be told that they are loved.
5. Two days ago, Greg killed several flying ants in his bedroom. He also sprayed a column of ants forming a colony along the kitchen baseboard. Yesterday he picked the evening newspaper off the porch and two black army ants scurried onto his hand. This morning, he found an ant crawling on a lollipop he had left in his shirt pocket. If any more insects appear, he is going to call Orkin Pest Control. He feels like the victim in a Hitchcock movie called The Ants. He is half afraid to sleep. The darkness may be full of tiny squirming things waiting to crawl all over him.


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The Arcana Wielders
There exists within each person, a power called Innocence. Innocence is a power that comes deep within the heart of its user, and is meant to be a reflection of one's inner self. Much like Tarot Cards, everyone's Innocence manifests itself into a form of Arcana, which starts in the form of The Fool. The Fool Arcana is one the represents the start of a journey, and beginnings. Like the number Zero, it's empty, but full of potential. However, after the awakening, Innocence manifests itself into a new Arcana, to display the growth of the user. However, there is one Arcana that is thought to be the strongest form of Innocence in existence. The World Arcana. An Arcana that is so powerful and rare, one user is born a century, and they possess the power to create a divine miracle, or destroy the entire fabric of reality. With the new wielder of the The World Arcana chosen by fate, you must protect them with your very life, or watch the world crumble beneath your feet....
So, this is basically a revival of an old RP i created a while ago called Innocence. However, there are several tweaks. There's more of a theme of Tarot Cards and Arcana, however, the story remains the same. A girl, known as Noel Dahlia, has awakened as the Successor to the The World Arcana, and you must protect her with your very life, or the world as we know it will come to an end.
1. All Bulba Garden Forum Rules apply here
2. What I say is Law
3. Romance, Language, and Violence is aloud, but keep it PG-13!
4. Try and be active!
5. No Bunnying, Trolling, MarySueing, God Modding, etc.
6 Have Fun!
Put Day Dream in your sign up if you have read and understand the rules!
Arcana Classes: In order to create some diversity among the cast, both in personality and in battle style, a list of Arcana will be available. This Arcana is often the basis of Innocence, and affects the general abilities of their users. For example, someone with the Priestess Arcana would excel at healing, while someone with the Chariot Arcana would excel at attacking. Only one character for each Arcana, and Arcana will be given on a first come, first served basis. Meaning the first one to claim an Arcana, gets it. Arcana can be reserved for up to 24 hours, but expire after 24 hours making them available again. Here's a list of Available Arcana. (To put this in simplest terms, this is sort of like a class system in Dungeons and Dragons or Final Fantasy.)
1. The Magician: In Tarot Readings, The Magician Arcana represents Talent, Skill, Creativity, and Concentration. Innocence Wielders of the Magician Arcana are skilled in all forms of elemental magic, and are fairly fast, with decent speed. But there defenses tend to lack, and they don't excel at attacking head on. The Wielders themselves are often free spirited, creative, and resourceful, often being able to create many ideas.
2. The Priestess (Taken By Naoto):Often thought of as the parallel to the Hierophant Arcana. In Tarot Readings, The Priestess Arcana represents Wisdom, Intuition, and Inner thought. Innocence Wielders of the Priestess Arcana typically excel at healing, but they are also capable of attacking using a single element of sorcery. The Wielders themselves tend to be soft spoken women, who are very intelligent.
3. The Empress: Often thought as the parallel to the Emperor Arcana, in Tarot Readings, the Empress Arcana represents motherhood, femininity, nature, and beauty. Innocence Wielders of the Empress Arcana often excel at Magic based attacks and projectiles, and they often decent defenses and healing capabilities. (But other Arcana Classes such as the Priestess or Lovers do better at healing.) The Wielders themselves tend to be beautiful strong willed woman who are fairly motherly, and often act as leaders.
4. The Emperor (Taken By Heroic Sociopath): Often thought as the parallel to the Empress Arcana, in Tarot Readings, the Emperor Arcana represents control, structure, and fatherhood. Innocence Wielders of the Emperor Class tend to excel at close range attacks, and being able to endure attacks, with decent speed. (But their speed is usually outclassed by other melee attackers such as the Chariot or Strength Arcana's). The Wielders themselves tend to strong willed men, who act as leaders, and tend to be in control of their own situation.
5. The Hierophant: Often thought as the parallel to the Priestess Arcana, in Tarot Readings, the Hierophant represents solidarity, tradition, and wisdom. Unlike it's sister Arcana, The Priestess Class who excel at healing, the Hierophant Class Wielders often excel at physical attacking, along with a certain form of elemental sorcery. The Hierophant Class Wielders themselves often are men with high intelligence, and are rather strong willed.
6. The Lovers: In Tarot Readings, The Lovers often represents bonds, relationships, and harmony. Innocence Wielders of The Lovers Class often excel at healing, and support skills, buffing their allies and healing any wounds. However, they often lack offensive capabilities. Wielders of The Lovers Class often are well liked and popular individuals, with a rather kind heart.
7. The Chariot (Take by DracoMan): In Tarot Readings, The Chariot often represents Willpower, Drive, and Victory. Innocence Wielders of The Chariot Class often excel at a front line assault, being able to attack with speed and strength, being able to pummel their foes into submission. However, the Chariot Class often struggles at attacking from a distance, and their defensive capabilities isn't the best, not being quite as strong as those of the Strength or Emperor Arcana's. However, along with the Devil Arcana, they are the fastest class. The Wielders themselves often are strong willed, and unyielding individuals, who can have a short temper sometimes.
8. The Strength: In Tarot Readings, The Strength represents, Courage, Patience, and Strength. Innocence Wielders of The Strength often excel at physical abilities, having all around above average defense, strength, and speed. However, their magic resistance is below average, and their magical aptitude is lower then average. The Wielders themselves are patient, strong willed, and generally fairly athletic.
9. The Hermit (Taken by Ludwig Beilschmidt: In Tarot Readings, The Hermit represents solitude and self awareness. Innocence Wielders of the Hermit Class typically excel at enduring magical attacks, having the highest magical resistance among the Arcana classes. They also use dark magic along with spells meant to sabotage the foe. However, Hermits tend to be rather slow, and often need to endure attacks before attacking themselves. The Wielders themselves often are quiet individuals who prefer solitude.
10. The Fortune: Often referred to as "The Wheel of Fortune". In Tarot Readings, Fortune represents luck, destiny, and cycles. Innocence Wielders of The Fortune Class often excel at attacking, but often have decent magical resistance to. They often use sorcery revolving around Light and Darkness, but they can attack with decent physical attacks depending on their weapon. The Wielders themselves are often observant individuals, who are well aware of the changing fates.
11.Justice (Taken By Naoto): In Tarot Readings, Justice represents, truth, fairness, and ideals. Innocence Wielders of the Justice Class often excel at support and buffs, physical attacks, and light based sorcery. They however, are fairly weak to Darkness Attacks, taking more damage from them then the other Arcana Classes. The Wielders themselves tend to be kind hearted people, who are passionate about fairness and their ideals.
12: The Hanged Man: In Tarot Readings, The Hanged Man represents Restriction, Suspension, and Sacrifice. Innocence Wielders of The Hanged Man Class often excel at handicapping their opponents, and dealing damage with physical attacks. However, their magical resistance is rather weak, and they have fairly weak magical capabilities.
13: The Death: In Tarot Readings, Death usually represents change and cycles. Innocence Wielders of the Death Class, often excel at handicapping the foe, physical attacks, and Darkness based Sorcery, However, they suffer more from Light Based attacks more then the other classes. The Wielders themselves have usually experienced a near death experience before, or have lost a loved one, with the occurrence changing them for the rest of their lives.
14: Temperance:: In Tarot Readings, Temperance represents balance, equality, and purpose. The Wielders of the Temperance of Arcana are the Jack-of-all-trades so to speak. They can have access to healing, support, physical, and magical skills, but they often don't excel at anything like the other classes, their main weapon being their versatility. The Wielders themselves tend to be calm individuals, who understand the importance of moderation.
15The Devil: In Tarot Readings, the Devil Represents Sexuality, Bondage, and Mischef. The Wielders of the Devil Class are offensive gems, being very speedy, and excelling at both Magical and Physical attacks. They can use any form of elemental magic, but they usually prefer Darkness and Fire, and their tied with the Chariot Class for being the fastest class. The down side to being so offensively capable, is their lack of defenses. They have the weakest defenses among the classes, and they often rely on healers to stay in battle for long. The wielders themselves often are mischievous jokers, with a slightly perverted and dark sense of humor.
16: The Tower: In Tarot Readings, the Tower Represents disaster and change. The Innocence Wielders of the Tower Class excel at great defenses, and powerful physical strength. However, their speed is rather slow, and their magical aptitude is very low. The Wielders themselves often are stoic individuals who understand that nothing will always remain the same.
17: The Star(Tailisu10): In Tarot Readings, the Star Represents Joy, Hope, and Renewal. The Wielders of the Star Class tend to favor Support and Magic centering around Ice and Light, and they typically excel at defense, while having low physical strength. The Wielders themselves often are cheerful individuals with a hopeful and friendly outlook on life.
18. The Moon: In Tarot Readings the Moon represents Mystery, Fear, and Illusion. The wielders of the Moon Class often excel at using Physical skills, along with Ice and Darkness based magic. The Wielders themselves often have a slightly melancholy outlook, but enjoy solving puzzles.
19. The Sun: In Tarot Readings, the Sun Represents Fun, Warmth, and Joy. The Wielders of the Sun Class often excel at using Physical Skills, along with Fire and Light Based skills. The wielders themselves typically are sunny and cheerful people, who can smile even in a bleak situation.
Sign Up Forms:
Name: (First and Last)
Age: (14 though 17, your still in high school)
Gender: (Male or Female)
Arcana Class: (Any free Class from the list above)
Appearance: (A description of what your character looks like. This RP takes place in the real world despite the fantasy themes)
Personality: (What is your characters personality like, should be like their Arcana Class description)
Family Members: (Tell me about their family members and their status, aka, living, deceased, missing, etc.)
History: Just 4 sentences on background, nothing major. Your character will be living in the city, Bell Ridge, and they attend the same high school as Noel.
Innocence: (What is your Innocence, and how does it work. Is it a weapon? A Power? Give me details!)
Spells/Skills: (5 Spells or Skills that reflect your Arcana Class, you'll learn more spells as the RP goes on)
Other: (What ever doesn't go anywhere else


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24 Products of the Year – the best of the What Hi-Fi? Awards 2014
The ultimate Christmas wish list? It might just be. These are the Product of the Year winners from each of the 24 product categories at the What Hi-Fi? Awards 2014.Fri, 17 Oct 2014, 03:07pm
Best TVs to buy in 2014
If you're in the market for a new TV, you're in luck. We've rounded up a collection of the best TVs you can buy in 2014, from budget to premium, 3D to 4K and OLED.Thu, 16 Oct 2014, 11:53am
Two brands, five Awards: the best TVs of 2014
Samsung and Sony dominate our list of the best 2014 TVs, with Award-winners at every size and price, and featuring our first 4K TV Award-winners.Tue, 14 Oct 2014, 02:40pm
Deals of the Week – TVs, wireless speakers, soundbars and more
It's the August bank holiday this weekend and that means – for many of us, at least – an extra day to spend at our leisure. And it's an ideal chance to start building that new hi-fi or home cinema system, or upgrade an existing set-up with some fresh new kit.Fri, 22 Aug 2014, 02:16pm
Latest TVs: Get more for less with our August issue – on sale now
The trickle of 2014 TVs has turned into a torrent; we test seven efforts from this year's launches to see which offers you the best home cinema experienceWed, 02 Jul 2014, 08:27am
We found 5 news for '


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Modern Fairy Tale Prelude to a Kiss at Las Vegas Little Theatre
* Additional fees apply.
The last date listed for Prelude to a Kiss was Friday March 4, 2011 / 8:00pm.
Most Popular Theater Event Nearby
Wicked: Broadway's Biggest Blockbuster Flies Back to Las Vegas
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Venue Details
Great choices of Chinese and Thai food in Chinatown.Picnic dining • Apr 14 2014 star this tip starred
Always easy parking and a cheerful, helpful staff.It Runs in the Family info • Nov 15 2013 star this tip starred
Reviews & Ratings
Featured review from Goldstar Member
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The show was very well presented and the actors were meant to play their parts. We really enjoyed it.
Quotes & Highlights
Prelude to a Kiss is titled after a torch song by Duke Ellington. In 1992, a film was made based on the play, starring Meg Ryan and Alec Baldwin.
Immediately after a young couple named Peter and Rita have exchanged wedding vows, an unknown elderly man asks to kiss the bride. As he does, Rita's soul and the old man's magically exchange bodies. Neither Peter nor the wedding guests grasp what has happened. Peter leaves the wedding with a woman he believes is Rita. During their honeymoon, he comes to realize that Rita's body is no longer inhabited by Rita's true personality. He must find the old man, and keep his love for Rita alive… despite the fact that she is now in an unattractive body.
Prelude to a Kiss features Andrew Eddins as "Peter;" Penni Mendez as "Rita;" and, Dave Pomeroy as "The Old Man." Other cast members include Micah Epstein, Valerie Carpenter Bernstein, Ryan Balint, Sue McNulty, John C. Hughes, Anthony Avery, Anne-Marie Somers, Tiara Coleman, Jay Somers, Steve Goldstein, and Ann Pomeroy. Directing this extraordinary journey through fantasy and reality is Gillen Brey.


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Indian Olympic Association fined $10,000 for withdrawing teams...Interestingly, the Indian contingent's chef de mission and Athletics Federation of India president Adille Sumariwalla told PTI that he was not aware of any such development. The post Indian Olympic Association fined $10,000 for withdrawing teams from Asian ... First Post.com, 4 weeks ago
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C.Rajshekhar Rao, The Associated Press Published Wednesday, September 24, 2014 9:31AM EDT INCHEON, South Korea -- The Qatar women's basketball team forfeited a match against Mongolia on Wednesday and is considering withdrawing from the Asian ...CTV News, 3 weeks ago Qatar forfeit basketball match in hijab row in Asian Games MENAFN, 3 weeks ago Asian Games: Indian Sikh basketball players break with religious tradition to play India TV, 3 weeks ago Women in Business: Stacey Allaster, Chairman and CEO of the Women's Tennis Association Huffington Post, 4 days ago
Sanathoi Devi talks about her Asian …
Sanathoi Devi with the bronze medal at the Incheon Asian Games The resolve of an athlete comes to the fore when the going gets tough. India's women wushu player Yumnam Sanathoi Devi showcased that in abundance at the 2014 Incheon Asian Games, as ...Yahoo! India, 1 week ago Incompetent sports bodies ruining players' zeal Meri News, 1 week ago Asian Games: Boxer refuses medal Asiaone, 2 weeks ago Blame the Indian Olympic Association, not Laishram Sarita Devi DNA India, 2 weeks ago
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Experienced Siperian Developer with Pharma Data Profiling experience Please contact us at 732-248-1900 ext 236 Job Role: • Applications Design… Glassdoor
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They have very good contacts and hence are able to get good projects. They do have a good marketing head who pushes your profile very hard.Cons
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March 27, 2014 - 16:02 GMT
scrap prices
Baltic Sea
Metal Bulletin's daily index for HMS 1&2 (80:20) scrap material delivered to Turkey went down slightly this week on weak demand in the country.
The index closed at $366.02 per tonne cfr on Thursday March
27, down by $1.45 per tonne day-on-day. Few deals were heard
this week as mills were mostly waiting until after the
country's mayoral elections on March 30 in the hope...
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WEEK IN BRIEF: London Metals Week; Bagri warning; copper surplus looms; destocking, financing weighs on nickel
Metal Bulletin looks back over the key market news following one of the biggest weeks in the metal industry calendar - London Metals Week.
LME WEEK: Nickel bulls react to price slump by highlighting fundamentals
The timing of this year's London Metals Week was unfortunate for nickel bulls.
HOTTER ON METALS: Warehousing is changing
Impala, the warehousing and logistics unit of Trafigura, signed a joint venture with Citic this week and announced it plans to delist from all but two London Metal Exchange-approved locations.
4th Asian Bauxite & Alumina Conference
29 Oct 14 - 30 Oct 14
30th International Ferro-Alloys Conference
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11 Nov 14 - 13 Nov 14
From Aluminium to Zinc...Search this free glossary on metals
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